Issue 40, 2019

Thermodynamic insights into the entropically driven self-assembly of amphiphilic dyes in water

Abstract

Self-assembly of amphiphilic dyes and π-systems are more difficult to understand and to control in water compared to organic solvents due to the hydrophobic effect. Herein, we elucidate in detail the self-assembly of a series of archetype bolaamphiphiles bearing a naphthalene bisimide (NBI) π-core with appended oligoethylene glycol (OEG) dendrons of different size. By utilizing temperature-dependent UV-vis spectroscopy and isothermal titration calorimetry (ITC), we have dissected the enthalpic and entropic parameters pertaining to the molecules' self-assembly. All investigated compounds show an enthalpically disfavored aggregation process leading to aggregate growth and eventually precipitation at elevated temperature, which is attributed to the dehydration of oligoethylene glycol units and their concomitant conformational changes. Back-folded conformation of the side chains plays a major role, as revealed by molecular dynamics (MD) and two dimensional NMR (2D NMR) studies, in directing the association. The sterical effect imparted by the jacketing of monomers and dimers also changes the aggregation mechanism from isodesmic to weakly anti-cooperative.

Graphical abstract: Thermodynamic insights into the entropically driven self-assembly of amphiphilic dyes in water

Supplementary files

Article information

Article type
Edge Article
Submitted
22 Jun 2019
Accepted
19 Aug 2019
First published
20 Aug 2019
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2019,10, 9358-9366

Thermodynamic insights into the entropically driven self-assembly of amphiphilic dyes in water

P. P. N. Syamala, B. Soberats, D. Görl, S. Gekle and F. Würthner, Chem. Sci., 2019, 10, 9358 DOI: 10.1039/C9SC03103K

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